Herbicidal composition and method employing thiazole derivatives

ABSTRACT

D R A W I N G A thiazole derivative having the general formula

United States Patent Fuillot et al.

[451 Aug. 28, 1973 22 Filed: Mar. 2, 1970 21 Appl. No.: 15,899

Related U.S. Application Data [63] Continuation-impart of Ser. No. 540,192, April 5,

I966, Pat. No. 3,551,442.

[52] US. Cl. 71/90, 71/82 [51] Int. Cl A01n 9/12 [58] Field of Search 71/90 [56] References Cited UNITED STATES PATENTS 2,755,285 7/1956 O'Neill et al. 260/3068 3,454,591 7/1969 Schulz et a1. 71/90 FOREIGN PATENTS OR APPLICATIONS 38/14593 10/1963 Japan 260/3068 OTHER PUBLlCATIONS Degering, An Outline of Organic Nitrogen Compounds, (Michigan) 1950, p. 438

Bhangava et 21]., Bull. Chem. 800., Japan, Vol. 38, pp.

Tefas et al., Chem. Abstracts, Vol. 54, Columns 17376-17377 (1960) Primary Examiner-James 0. Thomas, Jr. Attorney-McDougall, Hersh & Scott [57] ABSTRACT A thiazole derivative having the general formula and pesticidal compositions containing the same.

13 Claims, No Drawings HERBICIDAL COMPOSITION AND METHOD EMPLOYING THIAZOLE DERIVATIVES This is a continuation-in-part of our copending application Ser. No. 540,192, filed Apr. 5, 1966, now U.S. Pat. No. 3,551,442 and entitled Thiazole Derivatives and Herbicidal Compositions Containing Same."

This invention relates to a new family of compounds which are derivatives of thiazole and it relates also to the use of the thiazole derivatives as pesticides and especially as herbicides.

It is an object of this invention to produce and to provide a method for producing thiazole derivatives of the type described and the use of such thiazole derivatives as a pesticide and/or a herbicide.

The thiazole derivatives embodying features of this invention may be characterized by the formula in which X and Y are groups which may be identical one with the other or different from each other. X and Y are representative of such groups as hydrogen, halogen such as chlorine, bromine, iodine, thiocyanate, --CN, COOH, an alkoxycarbonyl group, NI-I,, OH, a hydroxyalkyl, alkyl or alkoxy group containing from one to four carbon atoms such as methyl, ethyl, propyl, butyl, ethoxy, methoxy and the like in which the hydroxyalkyl, alkyl or alkoxy group can be unsubstituted or substituted with a halogen, an aryl group such as phenyl, naphthyl, a halogenated aryl group, an alkaryl group such as benzyl, tolyl and the like, an alkoxy aryl group, a halogenated alkaryl group, a halogenated alkoxyaryl group, an aryloxy group, a halogenated aryloxy group and an alkoxyaryl group, an aryloxy group, a halogenated aryloxy group and an alkaryloxy group; in which Z is an atom selected from the group consisting of oxygen and sulphur: in which R, is a group such as hydrogen or an alkyl, alkynyl, alkoxy, alkenyl or alkenoxy group having from one to four carbon atoms, an alkylated acyl residue, a halogenated alkylated acyl residue, an aracyl, a halogenated aracyl (arylated acyl), an alkarylated acyl, or an alkoxyaryl ocyl group; in which R, and R, is a group selected from hydrogen, an alkyl group, an alkoxy group, an alkenyl group, an alkenoxy group or an alkynyl group in which the groups contain from one to four carbon atoms, an alkaryl residue, a halogenated alkaryl residue, an aryl group, a halogenated aryl group or an aryloxy group but in which R, and R are not both hydrogen in the same compound.

The compounds defined above, which fall within the scope of the invention, may be prepared by a number of synthetic methods depending somewhat upon the nature of the groups R,, R, and R The following will set forth typical examples of methods for the preparation of such compounds:

1. When two of the three radicals R,, R, or R, are hydrogen, for example when R, and R, are hydrogen while R, is an alkyl group, aryl group, or alkaryl group, a halogenated alkaryl group ora halogenated aryl group, two methods of preparation can be employed:

a. The reaction of an alkyl or aryl isocyanate or isothiocyanate with a 2-aminothiazole in which X and Y are substituted groups, as illustrated in the following equation:

b. The reaction of a monosubstituted carbamyl or thiocarbamyl halide, in which the is the following: chlorine, with a 2-aminothiazole in the presence of an agent which binds the acid liberated during the reaction, in accordance with the equation:

3. When R, is one of the groups selected from an alkylated acyl, halogenated alkylated acyl, arylacyl,

halogenated arylacyl, alkylatcd arylacyl and alkoxylated arylacyl and when R, and R are selected from one or more of the groups of hydrogen, alkyl,

aryl, alkaryl, halogenated aryl or halogenated alkaryl except that R, and R, cannot both be hydrogen in the same compound, the following may be employed:

The halide of an aliphatic or aromatic acid, preferably the chloride R,Cl, is reacted with thiazolyl or the thiazolylthiourea derivative prepared in accordance with method (1) or (2), as illustrated by the following equation: III

N-( Z-thiazolyl )-N -methylurea;

N-(2-thiazolyl)-N',N'-dimethylurea;

N-( 2-thiazolyl)-N'-methylN'-methoxyurea;

N-( 2-thiazolyl)-N '-phenylurea;

N-(2-thiazolyl)-N'-methyl-N-propenylurea;

N-(2-thiazolyl)-N'-benzoyl-N',N'-dimethylurea;

N-(2-thiazolyl)-Nmethyl-N-phenoxyurea;

N-( 2-thiazolyl )-N-butenyl-N -ethylurea;

N-(2-thiazolyl)-N-trichloroacetyl-N'-butylurea;

N-2(5-chlorothiazolyl)-N,N'-dimethylurea;

N-2(5-chlorothiazolyl)-N'-methylurea;

N-2(5-chlorothiazolyl)-N-methylthiourea;

N-2(5-chloro-4-methylthiazolyl)-N-phenylurea;

N-2(5-chloro-4-methylthiazolyl)-N'-methylurea;

N-2(5-chloro-4-methylthiazolyl)-N,N'-

dimethylurea;

N-2(4,5-dichlorothiazolyl)-N'-methylurea;

N-2(4,5-dichlorothiazolyl)-N,N-dimethylurea;

N-2(4-trifluoromethylthiazolyl)-N'-methyl-N'- methoxyurea;

N-2(4-trifluoromethylthiazolyl)-N-methylurea;

N-2 4( 2-chloroethyl)thiazolyll-N -ethylurea N-2( 5 -bromothiazolyl-N '-butynylu rea;

N-2(4-chlorothiazolyl)-N'-methylurea;

N-2(4-chlorothiazolyl)-N,N'-dimethylurea;

N-2(4-chlorothiazolyl)-N-monochloroacetyl-N'- methyl-N'-phenyl N-2(4-choromethylthiazolyl)-N',N-dimethylurea;

N-2(4-chloromethylthiazolyl)-N-methylurea;

N-2(5-thiocyanatothiazolyl)-N'-methylurea;

N-2(4-phenyl-S-thiocyanatothiazolyl)-N- propenylurea;

N-2(5-carbethoxy-4-methylthiazolyl)-N'- methylurea;

N-2(4-2-hydroxyethylthiazolyl)-N'-(2,4-

dichlorophenoxy)urea;

N-2(4-methylthiazolyl )-N '-methylurea;

N-2(4-methylthiazolyl)-N',N'-dimethylurea;

N-2(5-methylthiazolyl)-N-phenylurea;

N-2(5-methylthiazolyl)-N'-methylurea;

N-2(S-methylthiazolyl)-N,N'-dimethylurea;

N-2(4-methylthiazolyl)-N-methyl-N-methoxyurea;

N-2(4,5 -dimethylthiazolyl)-N '-methylurea;

N-2(4,5-dimethylthiazolyl)-N,N'-dimethylurea;

N-2(4-methoxy-5-chlorothiazolyl)-N-acetyl-N'- propenylurea;

N-2(4-p-chlorophenylthiazolyl)-N-methyl-N',N'-

dimethylurea;

N-2(4-p-chlorophenylthiazolyl)-N'-methylurea;

N-2(4-p-methoxyphenylthiazolyl)-N'-tolylurea.

The compounds described have been found to have exceptional herbicidal properties. For this purpose, they find widespread application for inhibiting the growth or even destroying of all kinds of plants, pests, such as weeds, brushwood and undesirable shrubbery.

The amount of the compound required to achieve the desired herbicidal effect will depend upon a number of factors such as the nature of the compound itself, the resistance of the species of plants, the composition of the ground, the state of growth of the plant at the time that treatment is effected and finally upon the destruction desired to be effected, that is, a complete kill or only a selective kill.

The compounds may thus be employed as a total herbicide or as a selective herbicide or as a growth regulator. There is a wide range of possible applications depending upon the chemical nature and dosage of the herbicidal compound utilized. The compounds may be applied either prior to the seeding or planting of the cultures or application can be made as a preemergence treatment after seeding but before the cultures or weeds break through the ground or as a postemergence treatment after the plants break through the ground. In general, the compounds may be applied at any stage of plant growth best adapted to the problem to be solved and the nature of the cultivated plants.

In practice, the substituted thiazolylureas or thiazolylthioureas of the present invention are utilized in amounts within the range of 0.1 to 30 kilograms per hectare and preferably within the range of 0.5 to 20 kilograms per hectare. The optimum dosage will depend upon the intended aim, the type of application, the nature of the plant pests intended to be destroyed and their stage of growth and upon the persistence of the desire herbicidal action.

An interesting property of certain of the thiazolylureas and thiazolylthioureas of this invention resides in the persistence of their herbicidal action. Compounds of the type described, when suitably formulated, remain effective to prevent weed growth from several weeks to several months. This effectiveness over a long period of time is a very desirable feature of the compounds of this invention since weed control can be maintained throughout the growing season.

Another surprising property of the compounds of this invention is the highly specific character of their action on vegetation. When applied in proper dosages, the compounds are effective to destroy certain weeds which are dicotyledoneae without damaging other cultivated species of dicotyledoneae. Weed plants belonging to the graminaceae family may be destroyed in cereal cultures like wheat, barley, oats and Indian corn, without harming such cultures. The thiazolylureas and thioureas of this invention may be employed alone or in mixtures such as solutions in organic solvents, or as dispersions or emulsions of the oil-in-water or water-inoil types or as suspensions in aqueous medium. They may be formulated into pastes or mixed with powders for dusting or they may be applied as granules in mixtures containing talcum, kaolin, or other suitable filler.

Such solutions, dispersions, pastes, powders or granules may be formulated to contain different proportions of the active component depending upon the intended use. As previously described, such compositions may be formulated to contain the active ingredient in an amount within the range of 0.5 to percent by weight of the composition.

The compounds of this invention may also be mixed with other additives which are also active or toxic with respect to plants. Certain of these additives may be in the form of solids, as represented by sodium chlorate or the borates or in the form of liquids such as tar oil derivatives (creosotes), substituted or unsubstituted phenols, crude oil derivatives such as kerosene, gas oil, fuel oil and the like. The compounds may be formulated with other useful additives such as fertilizers which contain the usual elements of phosphorus, potassium and nitrogen, with or without trace elements such as Fe, Mn, Zn, Mg, Co and Cu.

In accordance with an important feature of this invention, the thiazolylureas or thioureas may be combined to give a synergistic reaction with other known pesticides in the form of fungicides, bactericides, insecticides and herbicides to increase the biological activity. It is possible to formulate the treating composition to contain one or more of the pesticides described having different chemical structures and biological activities and which may be selected from the group consisting of nitrophenols, chlorophenols, chloronitrophenols, halogenated aryloxyalkylcarboxylic acids, phenylalkylcarboxylic acids, halogenated benzoic acids and derivatives thereof such as the corresponding salts, esters, amines, amides and imides, halogenated carbamates, substituted thiocarbamates and thiolocarbamates, esters of dithiocarbamic acid, alkyl isothiocyanates, monoor disubstituted amides; di-, trior tetrasubstituted aralkyl ureas, substituted triazines, aminotriazole, substituted benzothiazole, hydrazides, uracil derivatives, pyridinium salts, quaternary ammonium salts, inorganic herbicides such as bichromates, alkali metal cyanates, Na AsO NH SO NH etc., as represented by the following specific compounds: pentachlorophenol; dinitrocresol; dinitrobutylphenol; Na 2,4- dichlorophenoxyacetate; Na 2,3,6-trichlorobenzoate; Na monochloroor trichloroacetate; isopropyl N- phenylcarbamate; ethyl N,N-dipropylthiolocarbamate; N,N-dimethyldiphenylacetamide; N-phenyl-N,N'- dimethylurea; 2-chloro-2,6-bis(ethylamino)-s-triazine; 3-amino-l,2,4-triazole; 2,6-dichlorobenzonitrile; maleic hydrazide, 2-chlorobenzothiazole; 1,1 '-ethylene dibromide; 2,2'-bipyridinium; methyl isothiocyanate.

In accorance with another feature of the invention, modifications can be made of the various formulations to include one or more surface active agents of the anionic, cationic or non-ionic types, as represented by: Na alkylnaphthalenesulfonate, Na cetyl sulfate, Na oleyl sulfate, Na lauryl sulfate, Na N-methyl-N- oleyltaurate, Na oleyl isothionate, Na ligninsulfonate, Na dodecylbenzene-sulfonate, alkanolamides of fatty acids, Na di(2-ethylhexyl)sulfosuccinate, sulfonated monoglycerides from coconut oils, alkyltrimethylammonium chlorides, a1kylbenzyldimethylammonium chloride, cetyltrimethylammonium bromide, the methoxysulfonate of oleyldiethylmethylethylenediamine; lauryl polyethylene glycol ether; ethers from polyoxyethylene and alkylphenols, polyethylene glycol stearate, polypropylene glycol stearate, condensation products of polypropylene glycol and ethylene oxide, esters of polyethylene glycol and of tall oil acids, sorbitol monopalmitate, sorbitol monooleate, tris(polyoxyethylene)sorbitol monolaurate, tris(polyoxyethylene)- sorbitol monooleate; the condensation product of ndodecyl mercaptan with ethylene oxide.

The following examples of the preparation and use of the compounds of this invention are given by way of illustration, but not by way of limitation:

EXAMPLE 1 Preparation of N-2(5-chlorothiazolyl)-N'-methylurea To a thoroughly agitated solution of 9.5 grams of 2- amino-5-chlorothiazole in 35 ml dimethyl sulfoxide (DMSO), 4.8 grams methyl isocyanate is added dropwise with an accompanying rise in temperature to about 56 C. When the addition is finished, the mixture is cooled to 45 C. and maintained at this temperature for about one hour by the addition of heat, if necessary. The solvent is distilled off in vacuum and the residue is taken up in 500 ml of boiling acetone in the presence of vegetable characoal. The warm solution is filtered and white shiny crystals are formed in the filtrate upon cooling.

The dried crystals have a melting point of 271271.5 C. The yield of the compound is about 50 percent by weight calculated on the basis of the starting amine. The following is an analysis in percent by weight of the compound produced in accordance with this example as compared to the theoretical compound calculated for C -,H ClN OS:

H Cl S Compound of Example 1 31.83 3.19 18.39 16.70 Calculated 31.33 3.15 18.50 16.73

EXAMPLE 2 Preparation of N-2(5-chloro-4-methylthiazolyl)-N'-phenylurea 5 grams of 2-amino-5-chloro-4-methylthiazole is dissolved in 50 ml of CH CN. 4.1 grams of phenyl isocyanate is added dropwise at room temperature with an accompanying rise in temperature to 50 C. This temperature is maintained for two hours, the mixture is cooled and the precipitate is collected and dried. it is purified by recrystallization from CH CN and decolorized in the presence of vegetable charcoal. 6.75 grams of N-2(5- chloro-4-methylthiazolyl)-N'-phenylurea is obtained in the form of a white powder having a melting point of 252 C., providing a yeild of about percent by weight. The compound is given the empirical formula of C H CIN OS:

C H N Cl Compound of Example 2 49.34 3.76 15.70 13.25 Calculated 49.46 3.62 15.90 13.29

EXAMPLE 3 Preparation of N-2(5-methylthiazolyl)-N'-phenylurea To a suspension of 7 grams of 2-amino-5- methylthiazole in 50 ml of CH CN, 7.7 grams of phenyl isocyanate is added slowly with an accompanying temperature rise to about 48 C. The amine becomes dissolved during the course of the addition and the solution is maintained at 48 C. for about 20 minutes. In the course of the reaction, an insoluble product is produced until finally the whole mixture stiffens. The mixture is allowed to remain for about 4 hours after which the crystals are separated and dried and washed with CH CN and again dried in vacuum. 12.45 grams of N- 2(5-methylthiazolyl)-N-phenylurea is secured in the form of a white crystalline powder having a melting point of -l96 C. corresponding to a yield of about 87 percent by weight.

EXAMPLE 4 Preparation of N-Z-thiazolyl-N'-phenylurea The procedure corresponds to that of Example 3 except that 2-aminothiazole is employed instead of the 2-amino-5-methylthiazole. The product N-Z-thiazolyl- N'-phenylurea is obtained in the form of a fine white powder having a melting point of about 171 C. which melting point is raised to 173 C. after recrystallization from CH,COOH of 50 percent strength. The yield of crude product corresponds to about 96 percent. The following is the analysis of the compound as compared to the empirical formula C H,N,OS:

C H N S Compound of Example 4 54.78 4.14 19.16 14.62 Calculated 54.77 3.91 19.23 14.48

To a suspension of 10 grams of 2-aminothiazole in 25 ml of CH CN, containing two drops of triethylamine, 6 grams of methyl isocyanate is slowly added by poruing. The reaction is slightly exothermic and the temperature rises to about 66 C. At the and of the addition, the mixture is cooled to 50 C. and maintained at this temperature for 1% hours. The N-2-thiazolyl-N'- methylurea separates in the form of a white crystalline precipitate which is air dried and then dried in vacuum. The yield of crude product, having a melting point of 215 C., is 15.45 grams or about 78 percent. After recrystallization in absolute alcohol at -30 C., the melting point is raised to 218 C. A final product in the form of shiny white needles is obtained in an overall yield of 94 percent. The following is the analysis of the compound N-2-thiazolyl-N'-methylurea produced in accordance with this example as compared to the empirical formula C H N OS: i

C H N O S Compound of Example 5 38.20 4.49 28.73 10.18 20.40 Calculated 37.77 4.35 28.84 10.52 20.90

EXAMPLE 6 Preparation of N-2-( 5 -thiocyanato )thiazolyl-N '-methylurea 580 ml of CH CN is warmed to 80 C. and 33.6 grams of 2-amino-5-thiocyanatothiazole is dissolved therein. 17.1 grams of methyl isocyanate is added with constant stirring and the stirring is continued while the mixture is maintained at 80 C. for eight hours.

Upon cooling, the substituted urea precipitates in the form of a fine, slightly pinkish powder which is filtered and dried. Te crude N-2-(5-thiocyanato)thiazolyl-N- methylurea has a melting point of 225 C. and is secured in the amount of 38.9 grams or about 86.5 percent yield. Recrystallization in methanol yields a final product in the form of small shiny flakes having a yellow coloration and a melting point of 226 C.

The results of the elemental analysis of the compound as compared to the empirical formula C H N OS is set forth in the following table:

C H N S Compound of Example 6 33.63 2.82 26.15 29.92 Calculated 33.42 2.74 25.96 29.90

EXAMPLE 7 Preparation of N -2( 5-carbethoxy-4-methylthiazolyl)-N'-methylurea By proceeding in accordance with Example 1 but using as the reagents methyl isocyanate and 2-amino-4- methyl-5-carb-ethoxy-thiazole, the above compound is obtained having a melting point of 262 C. after recrystallization from absolute ethyl alcohol, corresponding to a yield of about 75.5 percent. The analysis of the compound produced furnished the following values compared to the empirical formula C H N O S:

H N O 8 Compound of Example 7 44.43 5.38 17.27 19.72 13.17 Calculated 44.03 4.83 17 .44 19.92 13.50

EXAMPLE 8 Preparation of N-2(4-methylthiazolyl)-N'-methylurea The procedure of Example 5 is followed but in which the reagents are methyl isocyanate and 2-amino-4- methylthiazole. The above compound is obtained in a yield of 93 percent having a melting point of 212 C. after recrystallization from Cl-l CN.

The results of the analysis of the compound produced by the example as compared to the empirical formula C H N OS is as follows:

H N O S Compound of Example 8 42.09 5.30 24.54 9.34 18.73 Calculated 41.81 5.08 24.83 9.32 18.67

EXAMPLE 9 Preparation of N-2(4-trifluoromethylthiazolyl )-N'-methylurea H N F S Compound of Example 9 32.00 2.69 l8.66 25.31 14.24 Calculated 32.23 2.88 I8.76 25.20 14.45

EXAMPLE 10 Preparation of -N-2(4-p chlorophenyltiazolyl)-N -methylurea The procedure is in accordance with Example 5 but the reagents employed are methyl isocyanate and 2- amino-4-(p-chlorophenylthiazole). A yield of 97 percent is obtained of the compound N-2(4-p-chlorophenylthiazolyl)-N'-methylurea, having a melting point of 232.5 C. after recrystallization from acetonitrile.

The analysis of the compound produced as compared to the empirical formula c l-l ClN OS is as follows:

C H Cl N S Compound of Example 10 49.34 3.76 13.24 15.69 11.97 Calculated 49.16 3.64 13.30 15.52 11.96

EXAMPLE 11 Preparation of N-2(5-chloro-4-methylthiazolyl)-N '-methylurea A mixture of 6.1 grams of 2-amino-5-chloro-4- methyl-thiazole chlorohydrate and 25 ml pyridine is heated to 3540 C. 2.1 grams of methyl isocyanate is added over a period of 15 minutes. The mixture is heated with stirring for three hours to 50 C. and it is then cooled and rapidly poured over 500 grams of ice. The precipitate formed is filtered and recrystallized from CH CN. A yield of percent is obtained of the compound N-2(5-chloro-4-methylthiazolyl)-N'- methylurea in the form of a white powder having a melting point of 237 C.

The analysis of the compound as compared to the empirical formula C H CIMOS is as follows:

C H N Cl S Compound of Example 11 35.04 3.92 20.43 17.24 15.59 Calculated 35 .06 3 .70 20.23 17.09 15.64

EXAMPLE 12 Preparation of N-2( 5 -chlorothiazolyl )-N '-methylthiourea pared to the empirical formula C fl ClN S z C H N Cl S Compound of Exam le 12 28.91 2.91 20.23 17.06 30.87 Calcu ated 29.56 3.0 20.17 16.59 31.12

EXAMPLE 13 Preparation of N-2( 5 -chloro-4-methylthiazolyl)-N ,N '-dimethylurea 38.4 grams of pyridine is mixed with 22.7 grams dimethyl-carbamyl chloride and cooled to 5 C. 29.7 grams of 2-amino-5-chloro-4-methylthiazole is added in small increments. The reaction is slightly exothermic so that the temperature rises to about 16 C. The materials are allowed to stand for one hour and then heated for three hours at 60 C. The mixture is then allowed to cool and poured into 1 liter of ice water with thorough stirring so as to prevent the formation of lumps. The product N-2(5-chloro-b 4-methylthiazolyl)-N',l dimethylurea is separated by filtration and recrystallized from 1.5 liters of CH COOH of 50 percent strength. The crystals are washed with water until made neutral and the resulting compound obtained in a yield of 42.5 percent has a melting point of 163 C.

The analysis of the compound as compared to the empirical formula C,H, ClN OS is as follows:

C H Cl S Compound of Example 13 38.26 4.59 16.15 14.59 Calculated 38.29 4.22 16.15 14.59

EXAMPLE 14 Preparation of N-2(4,5 -dimethylthiazolyl)-N'-methylurea By using the method of Example 5 but employing as reagents 2-amino-4,5-dimethylthiazole and methyl isocyanate, the compound N-2(4,5-dimethy1thiazolyl)-N- methylurea is obtained in a yield of 84 percent, having a metling point of l84.5 C. after recrystallization from acetone.

The elemental analysis of the compound as compared to the empirical formula C H N,OS is as follows:

C H N 0 Compound of Example 14 45.38 5.98 22.67 8.63 Calculated 45.33 5.66 22.97 8.83

EXAMPLES 15-20 Biological experiments and tests were conducted with various greenhouse plants using N-2(5- chlorothiazolyl)-N'-methylurea in four different dosages, as set forth in the following tables. Two techniques of treatment were employed, as follows:

a. the pre-emergence treatment, i.e. after seeding but before the plants break through the ground (see Tables 1 to 3);

b. the post-emergence treatment, i.e. after the plants have broken through the soil, when each seed has developed into a yound plant of between 5 to 15 cm in height (see Tables 4 to 6).

The active product was formulated into an aqueous suspension from a wettable powder containing 20 percent by weight of the active compound and applied to the plants by atomization.

The results noted and the evaluations are set forth in the following tables as percent of destruction of the treated vegetation.

TABLE 1 Pre-emergence treatment of several plants which belong to the graminaceae and were cultivated in a greenhouse, the results and evaluations being made 37 days after treatment doses in kyhectare Species of treated plants of active material Pre-emergence treatment of various plants which are dicotyledoneae and were cultivated in a greenhouse, the evaluations being made 37 days after treatment:

doses of the active Species of plant treated material in kg/hectare p PLrum mn'vum) 0 0 0 3 Tomatoes (Solarium esculentum) 0 0 0 Carrots (Daucus carolta) 15 100 100 Linseed (linum lm'talissimum) 20 100 100 100 Buckwheat (Polygomun fagapyrum) 98 98 100 100 Amaranth (Amaranthu: species) 98 100 100 100 Rape (Bram'ca napus) 100 100 100 100 In Table 3, the active product is applied in the form of a sludge containing 5 percent by weight of a wettable powder of N-2(5-chlorothiazolyl)-N'-methylurea.

TABLE 3 Results after 10 days Results ater 30 days doses in kgJhectare' doses in kg./hectare of active material of active material Plant species treated 10 15 20 30 10 15 20 30 Mustard (wild) (Sinapis amends)... 80 100 100 100 100 100 100 Great nasturtlum (Tropaeolum majus,

variety Nanum) 0 0 0 0 0 0 Oats (Avcna saliva) 40 75 75 100 100 100 100 For the great nasturtium, as recognizable from this table, no destruction occurred, but a slight phytotoxicity was noted starting with the dosage of 10 kg/hectare of the active material.

Tables 1 to 3 show that N-2(5-chlorothiazolyl)-N'- methylurea has exceptional herbicide effect which can destroy species belonging both to the graminaceae as well as to the dicolyledoneae. Thus it is applicable against a wide spectrum of plants. Furthermore, this herbicide enjoys exceptional efficiency because it is able to destroy up to 100 percent of such species such as slender foxtail, rape and buckwheat when employed in dosages as low as 0.5 kg/hectare in the preemergence treatment. This compound also exhibits a selective herbicidal action due to an unexpected and remarkable fact. For example, when applied in the dosage of 0.5 kg/hectare, 90 percent of the foxtail is destroyed whereas the wheat remains undamaged. This herbicide shows a good selectivity with respect to peas and tomatoes in pre-emergence treatment, whereas, at thesame dosage, other dicotyledoneae such as carrots, linseed and rape are completely destroyed. At dosages of 4 kg/hectare, all of the test plants with the exception of the peas and the great nasturtium, are practically destroyed. Of considerable interest is the fact that the compound can function as a total weed removal agent.

The following tables 4 and 5 present the results of post-emergence treatments of various plants whih are, respectively, graminaceae in Table 4 and dicotyledoneae in Table 5. The experiments were undertaken on greenhouse cultures with a wettable powder containing 20 percent of the active ingredient N-2(5- chlorothiazolyl)-N'-methylurea. The evaluations set forth in the tables were made 34 days after treatment.

TABLE 4 Species of plant Doses per hectare, in kg treated of active material Wheat 0 0 0 Barley 0 0 0 0 Wild Oats 0 O O 10 Oats 0 0 0 20 Indian corn 0 0 0 25 Rye grass 85 9O 96 Slender foxtail I0 92 98 98 Wild Millet 80 100 100 l00 TABLE 5 Species of plant Doses per pectare, in kg of treated active material 'P' s O 0 Q 0 Rape O O 0 5 Linseed S 20 35 70 Carrots 5 40 80 98 Buckwheat I5 60 65 90 TABLE 6 Post-emergence treatment of various plants with aqueous dispersions containing 5 percent by weight of the active material:

S cies of Doses per p ant treated hectare in Wild Great Oats kg of active Mustard Nasturmaterial tium Results after 5 l0 days 2.5 0 0 0 5 0 0 0 10 80 0 l5 80 0 20 80 20 Results after 30 8O 0 2O 10 one month: 2.5 loo 0 0 5 I00 0 20 10 I00 0 95 l5 l0() 0 100 20 100 100 30 100 0 100 It will be recognized from the above table that for the great nasturtium no destruction occurs at any of the dosages although a slight phytotoxicity appears with the dosage of 10 kg/hectare of active material.

The results set forth in Tables 4 to 6 indicate that post-emergence treatment with the herbicide destroys 92 percent of the slender foxtail when applied in a dosage of l kg/hectare and that it is still fully selective in that it does not destroy wheat, barley and wild oats even at twice the dosage. At a dosage of 2.5 kg/hectare, wild mustard is completely destroyed within one month after treatment whereas oats remains unaffected.

EXAMPLES 21-23 Field experiments were conducted with N-2(5- chlorothiazolyD-N'-methylurea as the active material applied to the plants in the same manner as described in Examples 15-20.

a. Barley in spring At the stage of development of three leaves, barley is treated by applying 0.75 to 1.25 kg/hectare of active material. The accompanying weeds were represented by goosefoot (Chemopodium species) and by wild radish (Raphanus raphanistrum). The effectiveness of weed removal was very good 64 days after treatment.

b. Wheat in autumn The pre-emergence treatment in dosages of 1.5 kg/hectare was employed and it was noted that after three months the weed-killing effect was selective with respect to wheat. Slender foxtail and wild radish were destroyed substantially completely.

c. With peas Treatment was made as soon as the plants broke through the ground by application of the active material in dosages of l to 2 kg/hectare. The selectivity was perfect in that 45 days after treatment, the herbicidal efficiency was exhibited by the fact that knotweed (Polygonum aviculare), black bindweed (Polygonum convulvulus) and goosefoot (Chenopodium species) were completely destroyed without harm to the pea plants.

EXAMPLES 24-27 The biological activity of N-2(5-chloro-4- methylthiazolyl)-N'-methylurea upon various plants in the greenhouse was tested with four different dosages, as indicated in the following tables. Two different treatments were employed, namely, a pre-emergence treatment after the seeding but before the plants broke through the ground, a post-emergence treatment after the plants had broken through the ground and when each plant was present as a young plant (seedling) which was approximately between 5 to 15 cm in height.

The active material was applied by spraying from an aqueous suspension containing 20 percent by weight of the active material as a wettable powder. The results observed are expressed in the following table in percent of destruction of the treated plants.

TABLE 7 5 Pre-emergence treatment of various plants which are graminaceae, setting forth observations 41 days after treatment Species of Doses in ltglhectare of treated plants active materials 10 Wheat O 0 0 Indian corn 0 0 0 0 Wild Millet 0 0 0 l Barley 0 0 0 70 l 5 Oats 0 0 10 25 Millet 0 0 l 98 Rye grass 0 90 100 Slender foxtail 0 5 55 95 TABLE 8 2O Pre-emergence treatment of various dicotyledoneae, observations being made 41 days after treatment Species of Doses in kg/hectare of treated plants active materials Peas 0 0 0 0 Green bean (Phasenlur vulgaris) 0 0 0 25 Tomatoes 0 0 0 25 Common sunflower 3O (Helianthus annular) O 5 0 Buckwheat 0 0 5 Rape 0 0 I0 98 Linseed 0 65 lOO I00 Carrots O 98 lot) 100 35 The following tables 9 and 10 set forth the results from post-emergence treatments of variuos praminaceae in Table 9 and dicotyledoneae in Table 10, in the greenhouse. The results are those observed 42 days after treatment. 40

TABLE 9 TZ S cies of Doses in kg/hectare of pifiits treated active materials 45 Indian corn 0 0 0 0 Millet 0 0 0 Wild Millet 0 0 20 30 Oats O 0 30 I00 Slender foxtail 0 0 70 90 Barley 0 20 50 100 50 Wheat 0 24 50 98 Italian wild rye grass 0 70 95 I00 TABLE I0 Doses in kglhectare of 5 5 Species of active material plants treated Peas 0 0 0 0 Rape 0 0 0 0 Sunflower 0 0 0 50 Green beans 0 30 40 40 Tomatoes 0 30 90 Buckwheat 60 60 60 Linseed 60 60 Carrots 60 8t) 90 I00 It will be seen from Tables 7 to 10 that a clearcut activity is achieved both for the pre-emergence as well as for the post-emergence treatments when application is made in dosages between 4 to 8 kg/hectare of the active material. In the preemergence treatment, a selective weed killing is observed in that wheat, Indian corn, green beans and peas remain undamaged (Tables 7 and 8) whereas the slender foxtail is destroyed in the amounts of 5595 percent and the Italian wild rye grass in the amounts of 90-100 percent. In the postemergence treatment, a selective weed killing is obtained without harm to Indian corn and peas (Tables 9 and I0) while foxtail is destroyed in amounts up to 70-90 percent and wild rye grass in amounts up to 95-100 percent.

EXAMPLES 28-33 According to the method used in Examples 15-20, the biological activity of several substituted thiazolylureas which form the subject matter of this invention were tested with respect to plants using a dosage of 8 kg/hectare of active material. Tables I] and 12 set forth the results obtained, expressed in percent destruction of the treated plants.

TABLE 11 Pre-eniergence treatment of various graminaceae in which the results set forth were observed 46 days after treatment Pro-emergence treatment of various dicotyledoneae, in which the results were observations made 46 days alter treatment Examples N -2 (5-ehloro-4- N-2(4-rnethylmethylthia- N-2(4-trifluoro- Active material thiaz0lyl)-N- z0lyl)-N,N- methylthiazolyl)- tested rnethylurea dimethylurea N-methylurea Species of plant tested:

Peas 20 0 95 Green beans-. 0 0 70 Sunflower. 95 0 Tomatoes. 20 40 100 Buckwheat 90 30 100 Rape... 85 60 100 Linseed. 95 95 100 Carrots- 98 100 100 Examples 29 and 32 show that treatment is selective in that it does not destroy wheat, Indian corn, oats and barley, green beans, peas and sunflower, whereas de struction is observed of slender foxtail up to 95 percent, Italian wild rye grass up to '70 percent and wild millet up to 80 percent.

The compounds of Examples 30 and 33 show herbicidal activity but without too much selectivity. All of the millet and rape are destroyed and only Indian corn remains fully resistant.

The compounds of Examples 28 and 31 are selective in that wheat, Indian corn, millet, barley and green beans are not destroyed while herbicidal effect in the order of 85 percent is secured with respect to rape.

EXAMPLE 34 Treatment is effectedin accordance with Examples 15-20 but at a dosage of 10 kg/hectare, using as the active ingredient N-Z-thiazolyl-N'-methylurea. The active ingredient completely destroyed millet in a preemel'gence treatment.

EXAMPLE 35 Preparationof N-(S-cyano 2-thiazolyl)N'-methylurea The same method as that described in Example 6 is used except that the reagents are 2-amino-5- cyanothiazole and methyl isocyanate. The desired compound is obtained with a yield of 82 percent. Its melting point is 273 C. and it crystallizes in the form of white shiny flakes.

EXAMPLE 39 Preparation of N-(4,5-dimethyl-2-thiazolyl)N',N'-dimethylurea Using the method of Example 13, the reagents being pyridine, dimethylcarbamyl chloride and 2-amino 4,5- dimethyl thiazole, a compound melting at 201 C. after beingrecrystallized in acetonitrile is obtained with a 45 percent yield.

The analysis for C H N OS IS THE FOLLOWING:

C H S N The analys1s for C H N, OS 1s the followmg. Theoretical 48m 657 1609 2109 Experimental 48.63 6.44 16.03 21.47 C H N S 48.24 6.50 16.23 Theoretical 39.55 3.32 30.75 17.6% E 'm nt l 39.41 3.25 30.67 17.5

" e a EXAMPLE 40 Pre aration of EXAMPLE 36 p Preparation of N-(5-methyl-2-thiazolyl)N-methylurea and methyl isocyanate, a compound of melting point in the range 2102l5 C. is obtained with a 75 percent yield.

The analysis for C H N OS is the following:

H O S N-(4,5-diethyl-2-thiazolyl)N'-methylurea Using the same procedural steps as in Example 5 except that the reactants are 2-amino-4,5 -diethylthiazole and methyl isocyanate, a compound of melting point 185 C. crystallizing in the form of white flakes is obtained with an 89 percent yield.

The following will illustrate the herbicidal effect of additional compounds of this invention. The compounds tested are:

I N-(S-carbethoxy 4-methyl 2-thiazolyl)N'- Theoretical 42.09 5.50 9.34 18.73 Experimental 42.23 5.06 9.52 18.81 methylurea 18-72 11 N-(S-chloro 2-thiazolyl)N-methylthiourea EXAMPLE 37 III N-(4,5-dimethyl 2-thiazolyl)N',N-dimethylurea Preparation of N-(4-chlor0methyl-2-thiazolyl)N'-methylurea IV N-(S-methyl2-thiazolyl)N'-methylurea V N-(S-bromo 2-thiazolyl)N-methylurea VI N-(S-chloro 4-methyl 2-thiazolyl)N'-methylurea VII N-(4,5-dimethyl 2-thiazoIyl)N'-methylurea VIII N-(4,5-dimethyl 2-thiazolyl)N',N'-

dimethylurea IX N(5methyl2-thiazolyl)N'-methylurea.

In accordance with the method of Examples 15 to 20, the biological activity has been tested on various plants of compounds I to V above at the dose of 10 kg/hectare of active product. The following table summarizes the results obtained which are expressed in per cent destruction of the treated vegetals.

reddish mass which is not distillable is obtained, the

Moreover, in pre-emergence treatment, compound II structure of which is confirmed by nuclear magnetic resonance measurement.

at 8 kg/hectare produced 100 percent destruction of oats, millet, barley, ray-grass, foxtail, carrots, flax, buck-wheat, Echinochloa crusgalli, tomato, and 15 percent destruction of Indian corn and peas.

It will be seen from the foregoing that a new series of compounds are provided which have shown marked ac- EXAMPLE 38 Preparation of N-(4-methyl-2-thiazolyl)N,N-dimethylurea tivity as a herbicide in managing plant growth and in the destruction of undesirable weeds and plants connected with plant growth. The compounds of this invention exhibit an important degree of selectivity with respect to their herbicidal activity with various plants and combinations of plants.

It will be understood that changes may be made in the details of formulation and application without departing from the spirit of the invention, especially as defined in the following claims.

We claim:

1. A herbicide composition containing a diluent and an effective amount of at least one thiazole derivative having the general formula wherein X and Y are selected from the group consisting of hydrogen, C, C, alkyl, alkoxy, and halogenated alkyl, Z is oxygen or sulphur, and R is selected from the group consisting of C, C alkyl and alkoxy and C, C alkenyl, alkenoxy and alkynyl.

2. A composition as claimed in claim 1 in which the composition is in the form of a solution of the active ingredient in an organic solvent.

3. A composition as claimed in claim 1 in which the composition is in the form of a dispersion selected from the group consisting of oil-in-water and watenin-oil.

4. A composition as claimed in claim 1 in which the composition is in the form of an aqueous suspension.

5. A composition as claimed in claim 1 in which the composition is in the form of a powder, with and without additional filler.

6. A composition as claimed in claim 1 in which the thiazole derivative is present in an amount within the range of 0.5 to 80 percent by weight.

7. A herbicide composition containing a diluent and 18 an effective amount of N-2(5-chlorothiazolyl)-N'- methylurea.

8. A herbicide composition containing a diluent and an effective amount of N-2(5-chloro-4- methylthiazolyl)-N'-methylurea.

9. A herbicide composition containing a diluent and an effective amount of N-2(5-chlorothiazolyl)-N'- methyl-thiourea.

10. A herbicide composition containing a diluent and an effective amount of N-2(5-chloro-4- methylthiazolyl )-N '-N '-dimethylurea.

11. A method for controlling undesirable plant life that comprises applying thereto a growth-controlling amount of a compound having the formula:

N Ti i NC-N wherein X and R are lower alkyl and Y is hydrogen or lower alkyl.

12. A method for controlling undesirable plant life that comprises applying thereto a growth-controlling amount of a compound having the formula UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent N8. 3,754,888 Dated August 28, 1973 Inventor(s) Jean-Claude -G llOt et ,1

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

column 2, line 6, cancel "is the following" and substitute halogen is preferably column 7, line 6, correct the spelling of "pouring"; line 8, change "and" to end column 9, line 39, omit "b" after "chlorocolumn 11, line 28, correct the spelling of llwh u 7 column 13, line 27, last column'headed 8,

change "25" to 0; line 36, correct the spelling of "graminaceae"; line 41, omit '12 after Table 9-.

Correct the spelling of the inventors names as follows:

Jean Claude Guillot Pierre Poignant Jacques De Bazelaire de Lesseux Signed and sealed this Llth day of June 197L (SEAL) Attest:

EDWARD I LF'LETCH'ERJR. C MARSHALL DANN Attesting Officer Commissioner of Patents FORM P0405) V USCOMM-DC 60376-P69 Q ".5. GQVIINIINT PRINTING OFFICE: "I! 0-3I-3Jl 

2. A composition as claimed in claim 1 in which the composition is in the form of a solution of the active ingredient in an organic solvent.
 3. A composition as claimed in claim 1 in which the composition is in the form of a dispersion selected from the group consisting of oil-in-water and water-in-oil.
 4. A composition as claimed in claim 1 in which the composition is in the form of an aqueous suspension.
 5. A composition as claimed in claim 1 in which the composition is in the form of a powder, with and without additional filler.
 6. A composition as claimed in claim 1 in which the thiazole derivative is present in an amount within the range of 0.5 to 80 percent by weight.
 7. A herbicide composition containing a diluent and an effective amount of N-2(5-chlorothiazolyl)-N''-methylurea.
 8. A herbicide composition containing a diluent and an effective amount of N-2(5-chloro-4-methylthiazolyl)-N''-methylurea.
 9. A herbicide composition containing a diluent and an effective amount of N-2(5-chlorothiazolyl)-N''-methyl-thiourea.
 10. A herbicide composition containing a diluent and an effective amount of N-2(5-chloro-4-methylthiazolyl)-N''-N''-dimethylurea.
 11. A method for controlling undesirable plant life that comprises applying thereto a growth-controlling amount of a compound having the formula:
 12. A method for controlling undesirable plant life that comprises applying thereto a growth-controlling amount of a compound having the formula
 13. The method of treating plants as claimed in claim 12 in which the compound is applied in a dosage ranging from 0.1 to 30 kg/hectare. 